JPH0232147A - Composite material of fluororesin and production thereof - Google Patents

Abstract

PURPOSE:To obtain a composite material having high strength, high modulus of elasticity and good slipperiness free from interfacial delamination by forming a fibrous structure of thermoplastic liquid crystal resin in a fluororesin. CONSTITUTION:A composite material of resin which comprises at least a thermoplastic liquid crystal resin and a thermoplastic fluororesin wherein the thermoplastic liquid crystal resin forms a fibrous structure in the fluororesin. The diameter of the fibrous material of the thermoplastic liquid crystal resin is <=10mu and has >=10 aspect ratio. A liquid crystal polyester or liquid crystal polyester amide is used as the liquid crystal resin. Tetrafluoroethylene, polyfluoroalkoxyethylene, etc., are used as the fluororesin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluororesin composite comprising a 11% plastic fluororesin and a thermoplastic liquid crystal resin (hereinafter referred to as TLCP), and a method for producing the same.

More specifically, the present invention relates to a l&fat composite characterized in that TLCP is dispersed in a thermoplastic fluororesin in the form of fibers, and a method for producing the same.

[Conventional technology]

Fluororesin has many advantages, such as excellent chemical resistance, heat resistance, and light resistance, and because it is slippery, it is difficult for dust to adhere to it.

[Problems that the invention seeks to solve]

However, fluororesins have the major drawbacks of being heavy and having extremely low strength. Although fluororesin has many characteristics, it has not been widely used because of its low absolute strength (not to mention its ability to disconnect).

Although methods such as highly stretching fluororesin have been studied, they do not achieve the same high strength as in the case of glass.
Although there are examples in which glass fibers are used as reinforcing materials, it is extremely difficult to uniformly mix glass fibers and fluororesin. This is because fluororesins generally have high viscosity. Another problem is that glass is easily degraded by fluorine decomposition products. Furthermore, the fact that the glass is highly resistant is also a big problem considering that the fluororesin has a high specific gravity. Note that several examples of reinforcing other polymers with TLCP have been disclosed, including Japanese Patent Application Laid-open Nos. 61-26656.

However, there is no suggestion that fluororesin be reinforced with TLCP, and blended products have unstable microphases, resulting in unstable physical properties.

[Means to solve the problem]

In view of the current situation9, the present inventors have arrived at the present invention as a result of repeated studies without being bound by conventional research concepts20 The present invention has the following configuration in order to solve the above-mentioned problems. .

(11) A resin composite consisting of at least a thermoplastic liquid crystalline resin and a thermoplastic fluororesin (C1) A fluororesin characterized in that the thermoplastic liquid crystalline resin forms a fibrous structure within the fluororesin Resin composite.

(2) The fluororesin composite according to item 1, wherein the thermoplastic liquid crystal resin fibrous material has a diameter of 10 μm or less and an aspect ratio of 10 or more.

(3) l or 2 in which the l&J fat complex is a fibrous material
The fluororesin composite described.

(4) The fluororesin composite according to any one of 1 to 3, wherein the resin composite is in the form of a chip.

(5) The fluororesin composite according to any one of 1 to 4, wherein the liquid crystal resin is a liquid crystal polyester or a liquid crystal polyester amide.

(6) 1 to 1 in which the fluororesin is at least 1 fl of the following:
5. The fluororesin composite according to any one of 5.

Tetrafluoroethylene, polyfluoroalkoxyethylene, copolymer of tetrafluoroethylene and hexafluoropropylene, copolymer of tetrafluoroethylene and ethylene.

(7) 1 to 60I with a tensile strength of 35kr/■- or more
, , the fluororesin composite described in any one of them.

(8) The fluorine-48 (fat complex) according to any one of 1 to 7, wherein the liquid crystal resin has a melting point higher than that of the fluorine IH fat by 20°C or more.

(9) The fluororesin composite according to any one of 1 to 8, wherein the liquid crystal resin fibrous material is infusible.

(II) The fluororesin composite according to any one of 1 to 9, wherein the number average molecular number (■) of the liquid crystal resin fibrous material is 13,000 or more.

(11) The fluorine-1-lipid complex according to any one of 1 to 10, wherein at least an alkali metal salt and/or an alkaline earth metal salt is contained and/or attached to the fluororesin.

(12) The fluororesin composite according to any one of items 1 to 11, wherein fine particles of at least one metal compound selected from iron, cobalt, and chromium are contained and/or attached to at least the liquid crystal resin.

(13) Liquid crystal resin and fluorine) Rule j1 is melt-molded to form a resin composite in which the liquid crystal resin exists in the form of fibers in the fluororesin. A method for producing a fluororesin composite, which is characterized by high-temperature heat treatment in flowing water or in a vacuum.

(14) At least an alkali metal salt and/or
Alternatively, a liquid crystal resin containing and/or adhering to an alkaline earth metal salt and 10,000 fluorine resin containing and/or adhering to the metal salt are melt-molded to form a resin composite;
A method for producing a fluororesin composite, which comprises performing a high-temperature heat treatment under a flow of inert gas at a temperature higher than the glass transition temperature of the liquid crystal resin or in a vacuum.

(15) A liquid crystal resin composite consisting of one liquid crystal resin and one fluorine resin is placed in an inert gas flow at a temperature higher than the glass transition temperature of the liquid crystal resin.
Alternatively, a method for producing a 4M fluorine resin composite, which is characterized in that the liquid crystal resin is made infusible by heat treatment at a high temperature in a vacuum and then at a temperature higher than the melting point of the liquid crystal resin.

(16) At least 5mM% of fine particles of at least one metal compound selected from iron, cobalt, and chromium are added to at least a liquid crystal resin, and the resin composite is formed by melt-molding with a fluororesin under vacuum or inert gas. A method for producing a fluorine-1-4-lipid complex, which comprises molding the liquid crystal resin and then heating the liquid crystal resin at a temperature above (melting point -50) C. and in an oxygen-containing atmosphere to infusible the liquid crystal 411 fat.

The present invention will be explained in further detail below.

According to the present invention, this can be done easily and at low cost.

It is truly surprising that a fluororesin composite that is revolutionary in quality, stable in quality, and lightweight can be produced.

Furthermore, in the so-called textile field, it is truly surprising that fluorine fibers with high elastic modulus and high strength can be produced with high reliability and at low cost.

First, in Section 7, the polymer constituting the resin composite of the present invention will be described.

First, we will discuss TLCP.

The TLCP according to the present invention is a thermoplastic and liquid crystal moldable polymer. That is, it is a TLCP in which the mesogen group is in the main chain.

There are various types of such TLCPs, and they can be broadly classified into those made of aromatic polyester and those made of aromatic polyester amide.

There are various types of polyarylates, and conventionally known ones can be used.

It is not particularly limited.

Particularly preferred are TLCPs consisting of the following structural units. Namely here.

X is hydrogen.

halogen.

A with carbon number 4 or less Represents a rukyl group.

Here, Σnl=100. Particularly preferably, nl in each structural formula is 4 or more.

In addition, in each formula, various types of w!, including halogen, etc.
Substituents may be added, and the compounds shown above are particularly preferred because they can be easily melt-molded with the modified polyester of the present invention, and are also easy to bind into composite fibers with high strength and high modulus.

Similarly, conventionally known liquid crystal polyesteramides can be used without any limitation, and those shown in the following structural formula are particularly preferred. That is, here, X cannot be hydrogen, halogen, or an alkyl group having 4 or less carbon atoms.

Here, X represents hydrogen, halogen, or an alkyl group having 4 or less carbon atoms.

Here, in each structural formula, Σn! =100. Particularly preferably, nl of each structural formula is 15 or more. Moreover, each formula may have various substituents added thereto, including halogen, etc. Those shown in these formulas have melt moldability and high strength like TLCP made of polyarylate.

Such TLC:P is thermoplastic in nature. When heat resistance is particularly required as a resin composite, T
It is preferable that the melting point of the LCP is 20° C. or more higher than that of the fluororesin, and it is particularly preferable that the TLCP is infusible.

In addition, when strength, 9, and elastic modulus are particularly required as a 1-fat composite, the number average molecular weight of TLCP is preferably high to some extent, and more preferably, the number average molecular weight m is 13,000 or more. Particularly preferred is 30,000 or more. T.L.C.
When the number average molecular weight of P reaches such a value, both strength, modulus of elasticity, and elongation become high. Therefore, the strength as a 4M fat complex! This is preferable because the monosexuality rate also increases.

Next, the other essential polymer of the present invention, fluorocarbon resin, will be described.

The fluororesin is not particularly limited as long as it is a thermoplastic fluororesin, and conventionally known fluororesins can be widely used and are not particularly limited, and particularly preferred ones include:
Tetrafluoroethylene, polyfluoroalkoxyethylene, copolymer of tetrafluoroethylene and propylene hexafluoride, copolymer of tetrafluoroethylene and ethylene, vinylidene fluoride, and
Examples include copolymerized ethylene tetrafluoride containing chlorine in part.

Particularly preferred fluororesins include fluororesins with higher melting points. That is, examples thereof include tetrafluoroethylene, polyfluoroalkoxyethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, and copolymers of tetrafluoroethylene and ethylene. When such a fluororesin is used, not only the resulting resin composite has high heat resistance, but also the resin composite of the present invention can be produced stably. Furthermore, it is particularly preferable because the resin composite of the present invention can be processed stably even when it is further processed.

Furthermore, since the melt viscosity of polyethylene tetrafluoride, polyperfluoroether, etc. is extremely high, it may be difficult to melt-mold them, so it is also very effective to melt-mold them by adding a plasticizer etc. as appropriate. .

Although the present invention uses these two types of polymers as essential constituent components, other polymers may equally well be used as constituent polymers.

The one-mura fat composite of the present invention is made of a combination of such polymers, and can take various forms. In the resin composite of the present invention, it is preferred that the TLCP is substantially covered with a fluororesin, that is, a large number of islands are dispersed within a core-sheath matrix polymer. So-called polymer array type.

The aspect ratio (length/diameter ratio) of the dispersed fibers is 10.
The above polymer blend type and the like are particularly preferred. And T.L.
CP is in a fibrous form among such fluororesins. The m-pyramidal shape is not particularly limited, and all so-called Sa fibers are included.

That is, it does not matter whether the fibers are continuous fibers, fibrillar fibers, or the like. However, the aspect ratio of such fibrous materials is preferably at least 10 or more, particularly preferably 100 or more. When the aspect ratio increases, the resulting resin composite has high physical properties. In addition, it has extremely high physical properties especially when it is made into fiber or FRP processed from it. If the aspect ratio is less than 10, the resulting fiber is weak and weak even when processed into a composite.Conventional polymers have high flexibility, so there was no problem even with a low aspect ratio. In the case of TLCP, it becomes very weak.

Furthermore, as for the shape of the dispersed TLCP fibers, it is particularly preferable that the fibers are continuous.

Its diameter is also uniform.

Continuous fiber form gives high strength Fr? It becomes P. In particular, when the resin composite of the present invention is in the form of ta fibers, its strength can be increased. Further, the strength of TLCP dispersed in the fluororesin can be easily increased. Therefore, the strength of the 4M fat composite can also be increased.

It is preferable that the thickness of the TLCP extending from the fluororesin that is the matrix polymer is not very thick, and the particularly preferable diameter of the fibrous TLCP is 20 μm or less.

More preferably 10μ.

Particularly preferred is 5μ or less. The aspect ratio and diameter of the TLCP can be easily measured by removing the matrix polymer 1/≠#== and continuously observing the cross section.

TLCP with a small diameter not only provides a resin composite with high strength, but also provides a particularly good surface of the resin composite. In addition, the impact strength is particularly high. Moreover, the physical properties become stable. This tendency is particularly noticeable when highly elastic TLCP is dispersed in a fluororesin.

Further, it is preferable that the number of TLCPs in the 4M resin composite is large. If the number of fibers is large, external force is dispersed, so that a high strength product can be obtained.

If the resin composite is fibrous, it is preferable that three or more fibers are dispersed per cross section, particularly preferably five or more fibers, and still more preferably ten or more fibers. In addition, such TLC
The P fibrous material is preferably highly oriented and has an elastic modulus as high as possible, preferably 4 t/- or more, more preferably 6 t/- or more, particularly preferably 10 t/- or more. It has an elastic modulus of .

Further, the elongation is preferably 0.6% or more, more preferably 1% or more, particularly preferably 1.6% or more.
Such a material results in a good resin colored product.

The form of the resin composite of the present invention is not particularly limited, and may take any form such as fibrous, chip, flake, block, or film.

Further, forms in which these are further processed may also be taken. It can be selected depending on the purpose. Particularly preferred are fiber-like, chip-like, and film-like L-'a. In the case of fibers or films, the strength of the resin composite can be increased.

In addition, it is easy to handle, especially by layering the 1-gold complex of the present invention.
When used as RP, there are advantages such as 9 that strength control is easy. Further, in the case of a chip shape, the resin composite of the present invention can be further processed into various shapes, which is particularly preferable.

The tensile strength of the resin composite of the present invention is preferably 35+r/total or more, particularly preferably 70 kg/J or more.Resin composites with such values can be widely used, so they are particularly preferably 0M. Such a high-strength fluororesin composite can be produced by adopting the structure of the present invention in each case.

The form of the combination of TLCP and fluororesin in the resin composite of the present invention should be determined depending on the purpose and use.

That is, it should be determined by taking into consideration the affinity between TLCP and M-on-fluorine resin, +IA degree, elongation, melting point, thermal decomposition point, process passability, etc.

If the resin composite of the present invention is used as a so-called TA fiber, it is preferable that the melting points of TLCP and fluororesin are close to each other, and it is also preferable that the affinity is particularly high. If used as a material for FRP, etc., it is preferable that there is a certain degree of melting point difference between the two.
The difference in melting point between TLCP and fluororesin is 20°C or more, more preferably 40°C or more, particularly preferably 50°C.
There is a difference in melting point of more than 10%.

With such a difference in melting point, the resin composite of the present invention can be easily reinforced with 41 fatty fibers (TLcp fibrous material in the matrix polymer). P can be made.

Next, regarding the ratio of TLCP and fluororesin, the single value is also the objective.
The latter should be selected appropriately depending on the purpose. However, in general, it is preferable that the TLCP is 5% to 95% by weight, and if it is less than 5% by weight, the reinforcing effect of the TLCP often decreases.

On the other hand, if it exceeds 95% by weight, the fluororesin is often destroyed, which is a problem not only as a product but also as a process.

However, JII' for fluorine using a resin composite containing a high proportion of TLCP as a master resin composite? This does not apply when added to.

Therefore, the upper limit should be determined as appropriate, taking into consideration the purpose, processability, etc.

Note that the resin composite of the present invention may consist of only TLCP and fluororesin, but may also contain other polymers, plasticizers, light stabilizers, antistatic agents, terminal stoppers, fluorescent whitening agents, JI retardants, and antiaging agents. etc. may be contained.

Further, inorganic substances such as rm titanium, iron oxide, carbon black, etc. may be contained.

In addition, in order to improve the compatibility between TLCP and fluororesin, and especially to improve the melt moldability of fluororesin, various additives such as low molecular weight tetrafluoroethylene and mineral oil are added. Tari, TLCP.

It is also particularly preferred to modify the fluororesin. Particularly preferable third components include the following.

Part 1: Alkali metal salts, alkaline earth metal salts, Part 2
: Fine particles of metal compounds of iron, cobalt, and chromium.

It is particularly preferred that an alkali metal salt, an alkaline earth metal salt, etc. be attached to and/or contained in at least the fluororesin, and an alkali metal salt, an alkaline earth metal salt, etc. may be attached to and/or contained in the TLCP. Particularly preferred metal salts are potassium and sodium salts. Such salts include both inorganic salts and organic salts,
Both can be used. That is, inorganic salts such as potassium iodide and organic salts such as potassium alkyl phosphate are particularly preferred.

Such salts may be added during molding of the resin composite, or may be adsorbed after molding.However, in the case of organic salts, they may decompose during molding, so when adding them during molding, it is important to ensure that they are resistant to molding. It is necessary to limit the

As for the amount added, just a little bit is fine, 0.05 per mm of TLCP! lli% to 5% by weight is preferred.

If the amount is too large, problems such as deterioration of the physical properties of the resin composite will occur, so it is preferable to select from the range of 0.05 m1% to 53111%.
It is preferable to add a so-called surfactant at the same time.

The advantage of attaching and/or containing such alkali metal salts, alkaline earth metal salts, etc. is that the strength of the resin composite can be easily increased. That is, the strength of TLCP can be easily improved in a short time by processing under a high-temperature vacuum or in an inert gas such as nitrogen gas, so that the strength of the resulting tree-nh composite is also increased.

Next, it is also preferable to contain and/or adhere fine particles of metal compounds of iron, cobalt, and chromium to at least the TLCP. These are preferably at least 1mM% or more.The advantage of containing and/or attaching these is that the heat resistance of TLCP is increased. At the same time, light resistance is also improved.

Next, the method for producing the IH fat complex of the present invention will be described. T.L.
Composite molding of CP and fluororesin. Conventionally known methods can be used as the composite method, and there are no particular limitations. That is,
Typical examples include the core-sheath melt molding method, the so-called polymer array method, the so-called one-part exfoliation type fiber manufacturing method, the side-by-side method, the micro-division method using a static mixer, etc., and the polymer blend method. It is. And particularly preferred are the so-called.

The polymer array method and the core-sheath melt molding method are methods for producing two-part peelable fibers. By using such a method, TLCP can be easily made to have high strength and high elastic modulus. Furthermore, the ratio of TLCP and fluororesin is always constant down to the microscopic structure, resulting in a highly reliable 4!1 fat composite. On the other hand, the polymer blend method has the advantage that the number of TLCPs in the fluororesin can be increased relatively easily. In addition, in the case of the polymer blend method,
In order to increase the aspect ratio, TLCP and fluorine 4N
It is necessary to limit the viscosity difference and mixing ratio of fats.

In other words, it is preferable to keep the viscosity within 2 times, and the mixing ratio is TLCP/fluororesin-4.
It is preferable to set it to 0/60 - 60/40.

When the 4M resin composite of the present invention is produced by melt molding, it is preferable to take it off at a certain rate.By doing so, not only the resin composite but also the TLCP can have high strength and high elastic modulus. Furthermore, applying an electric field or a magnetic field during melt molding is also a particularly preferred method.

The composite melt molding method of TLCP and fluororesin is affected by the polymer type, metal atmosphere, melting time, discharge speed, etc., so it is important to set conditions appropriately. That is, it is particularly effective to use a heating cylinder, a heat retaining cylinder, etc.

In addition, as an unexpected effect of the present invention, in particular, the core-sheath melting method,
When the polymer array method is used, it has the advantage of increasing the speed of melt molding. In addition, not only TLCP but also the elastic modulus and strength of the resin composite can be made higher than when TLCP is spun alone.

In addition, when a particularly high-strength resin composite is desired, it is preferable, particularly preferably, that the resin composite thus obtained is subjected to a high temperature treatment at a temperature equal to or higher than the glass transition temperature of the TLCP under a flow of an inert gas such as nitrogen or under vacuum. It is preferable to process at a high temperature of 200°C or higher.By doing this, it is not uncommon for the strength of the resin composite to become a high-strength +i resin composite that is more than twice as strong as after molding. When it is desired to shorten the processing time, it is preferable to contain and/or adhere at least 1% to 5% by weight of an alkali metal salt or alkaline earth metal to the fluororesin and to perform high temperature treatment. By doing so, the high-temperature heat treatment time can be reduced to less than half that of treatment without additives.

Incidentally, such a salt may be added at the time of melt molding, or may be added after forming the tree composite.

In particular, when the salt is an organic salt, it is preferably added later as a resin composite.

In addition, especially when it is preferable that the TLCP in the resin composite is infusible. It is preferable to perform such high-temperature heat treatment and then further process the resin composite at a high temperature. That is, the TLC
It is preferable to process at a temperature above the melting point of P. In addition, TLC
Since the melting point of P increases with heat treatment, it is necessary to check the melting point of TLCP after high-temperature heat treatment before heat treatment. By doing this, TLCP can be made infusible in the fluororesin resin composite. Whether or not TLCP has become infusible can be easily confirmed by measuring the fluororesin resin composite with a differential scanning calorimeter (DSC) or the like.

Also, improved heat resistance near the melting point of TLCP. Further, for infusibility, it is preferable that at least TLCP contains and/or adheres fine particles of at least one metal compound of iron, cobalt, and chromium. Such fine particles are added during melt molding of the resin composite. It should be noted here that when such fine particles are added and melt-molded, TLCP may become infusible. Therefore, when adding such fine particles, it is essential to seal with an inert gas such as nitrogen gas or to melt-form under vacuum. The amount of such fine particles added is at least III% or more based on TLCP, particularly preferably to
It is preferable to provide at least ai%. Furthermore, it is preferable that the fine particles that can be used as the fine particles of the present invention are as fine as possible. Particularly preferred are fine particles with a diameter of 0.1 or less. Note that short whiskers and the like are also included in the fine particles of the present invention.

In this way, the resin composite to which the WX particles have been applied is then
Heat-treated in an oxygen-containing atmosphere at a temperature higher than (melting point -50)℃ of LCP. The maximum processing temperature is (melting point + 20)°C. The processing time varies depending on the type of 'l'LcP. f of fine particles! I
Although it varies greatly depending on Jt, amount of oxygen, etc., it is necessary to process for 1 second or more.

Of course, this is true. Fine particles are added to the TLCP resin composite to form a resin composite.

Next, the TLCP is subjected to solid phase polymerization by high temperature heat treatment using the method described above. next. Even when treated in air at temperatures above (melting point -50)'C, TLCP becomes infusible. The fluororesin of the present invention; the sesame composite has high strength, high modulus of elasticity, high moldability, and high toughness, so it can be used in the following wide range of applications.

High-strength fluorine heat 11 fat fibers, reinforcing materials, reinforcing materials for optical fibers, propellers, window frames, blinds. Baking materials for rust prevention materials, chemical resistant materials. Materials for parabolic antennas, weatherproof reinforcement materials,
High strength water repellent material, sink, kitchenware system kitchen. Materials for semiconductors. Base material for cast-in heaters, cast-in frying pans, VF-included heaters, concrete reinforcement materials.

Marine concrete reinforcement, marine materials, Hermefu l., molding chips. High strength molding chip, FRP.

Base material for FRP, base material for electrical insulation. Base material for printed circuit boards.
rope. Protective material. Screen gauze. Pharmaceutical filters, filters, reinforcement materials for filters, base materials for fiber blends with carbon fiber, etc., high-strength film materials, military materials, wind stabilizers, roofing materials.

Roofing materials, tents, and temporary roofing materials, especially in snowy areas.

Wall materials, desk 2 plywood surface materials, high-strength cloth, various frames, bicycle base materials, etc., superconducting materials, oil-less bearings, cleaning brushes, gaskets, backing materials, cartridges9. Shear fabrics for filters, paper making, printing, etc., demister-9 sliding members, base materials for oil-less bearings, etc.

The present invention will be explained in more detail with reference to Examples below.

It goes without saying that the present invention is not limited to these embodiments.

〔Example〕

Example 1 A resin composite consisting of polymer array fibers having TLCP as an island component and fluorine 10,000 fat as a sea component was prepared as described below. There were no particular problems with yarn reeling.

△, Silk spinning conditions ■ Sea component = copolymer resin of tetrafluoroethylene and hexafluoropropylene.

■Island component (TLCP): Liquid crystal polyarylate manufactured by Celanese, USA Product name Vectra Type A900 ■Island/Sea - 50150 ([Ratio)] ■Number of islands - 70 [Phase] Spinning temperature - 305℃ ■Spinning speed - 150 m/min ■Stretching ratio: None.

B. Characteristics of the obtained fiber ■ Fineness of resin composite fiber = 10 denier (hereinafter referred to as d) 0 Strength - 4.1 g/d (66 kg/■ l) ■ 1 Width - 2.1% ■ Elastic modulus = 220 g/d (3,5t/■t)0 Aspect ratio of TLCP in fiber -100 or more (T
Since L CP is continuous, it is practically infinite. ) The number average molecular weight of TLCP was approximately 1,60,000.

That is, a fluororesin composite fiber made of fluorine 10,000 resin and TLCP with high strength and high elastic modulus was obtained.

Example 2 When the fiber of Example 1 was heat treated under a nitrogen gas flow at 250° C. for 10 hours, a fiber having the following characteristics was obtained.

■Fineness of resin composite fiber -10d ■Strength = 10.3 g/d (166kg/uF)■
1 Moderate = 3.2% ■Modulus of elasticity - 340g/d (5.5t/■l) Aspect ratio of TLCP in 0 fibers 100 or more (TL
Since CP is continuous, it is practically infinite. ) The number average molecular weight of TLCP was approximately 58,000.

That is, a fluororesin composite fiber made of a fluororesin and TLCP with high strength and high modulus of elasticity was obtained. Also.

The melting point of TLCP was 312°C as measured by DSC.

Example 3 Only the ratio of island component and sea component in Example 1 was changed to 80.
．． The sea ratio was changed to 20 and yarn spinning was carried out in the same manner as in Example 1.
Next, when solid phase polymerization was carried out in the same manner as in Example 2, the strength of 9 was 14.
．． A fluororesin composite fiber with an extremely high strength of 2 g/d was obtained.

Example 4 The fibers of Example 1 were condensed and passed through a heating furnace at 320°C.
Next, pass it through a die at 280℃ to make a firm zero order of about 1
(Canto to J and tipped.

Next, this chip was treated under a nitrogen stream at 250°C for 20 hours, and then passed through an extruder at 325°C.
A plate-like product about 2 inches thick was made. The bending strength of the wooden board is about 5 times that of one made only of fluorine 10,000 fat, and the impact strength of Eyeshift 11 is about 10 times.

It was expensive.

In addition, the fact that TLCP in the wood board is infusible indicates that
This was confirmed by measuring C.

Example 5 2% by weight of potassium iodide was added to the fluororesin of Example 1, and the mixture was passed through an extruder to form chips.

Next, the chips were made into a sea component and treated in the same manner as in Example 1 to obtain the following fibers.

8.Characteristics of i#ed fiber ■1 Fineness of degreased composite fiber = 12d ■ Strength - 3.6 g / d (61 kg / fin) ■ Elongation -
2.0% ■ Elastic modulus - 220g/d (3.5t/dragon) 0 Aspect ratio of TLCP in fiber - 100 or more (TLCP is continuous, so it is practically infinite.) Note that the number average molecular weight of TLCP was about 16,000.

That is, a fluororesin composite fiber made of a fluororesin and TLCP with high strength and high modulus of elasticity was obtained. In addition.

Organic phosphate potash was used as the take-up oil.

Next, this fiber was heat-treated for 2 hours under a nitrogen gas flow at 250° C. in the same manner as in Example 2, to obtain a fiber having the following characteristics.

■ Strength = 9.2 g/d (148 kg/mi) ■ 1 Moderate - 2,7% ■ Elastic modulus = 370 g/d (5,9 t/l) Aspect ratio of TLCP in 0 fibers = 100 or more (T L
Since CP is continuous, it is practically infinite.

) That is, a fluororesin composite fiber made of a fluororesin and TLCP with high strength and high elastic modulus was obtained in a short time.
The melting point of P was 308°C as measured by DSC.

Example 6 15% by weight of magnetic iron oxide was added to the TLCP of Example 1, passed through an extruder and made into chips.Then, the chips were made into island components and treated in the same manner as in Example 1. hand,
Further, in the same manner as in Example 2, the fibers were subjected to surface phase polymerization and then treated in air at 250° C. for 1 hour to obtain a fluororesin composite fiber in which the following TLCP component was made infusible.

■ Fineness of resin composite fiber - 8 d ■ Strength - 7.8 g/d (61 kg/m) ■ Elongation - 2,
0% ■Modulus of elasticity - 200 g/d (3.2 t/l) Aspect ratio of TLCP in 0 fibers - 100 or more (TL
Since CP is continuous, it is practically infinite. ) Example 7 Production of TLCP and fluororesin were carried out as described below. There were no particular problems with the process.

8. Silk spinning conditions Sea component: Same as Example 1. Island component (TLCP): A liquid crystal polyester amide was prepared according to the method disclosed in Example 1 of Japanese Patent Publication No. 62-50496. ! 11. A prototype liquid crystal (grease-resistant) polyesteramide was produced using acetoxyanilide and butoxyterephthalic acid as raw materials.The liquid crystal initiation temperature of this polymer was approximately 220°C.

The melting point was approximately 290°C.

@,%/i-50/50 (ffll ratio)■Number of islands-
36 ■ Spinning temperature = 315°C ■ Spinning speed - 1000 m/min ■ Stretching ratio = None.

B. Properties of the obtained fiber ■ Fineness of resin composite fiber - 15 d 0 Strength - 3.3 g/d (53 kr/m #) ■ Elongation - 2
, 2% ■ Elastic modulus - 190 g/d (3,1 t/Rin J) Aspect ratio of TLCP in 0 fibers = 100 or more (TL
Since CP is continuous, it is practically infinite. ) The number average molecular weight of TLCP was approximately 17,000.

That is, a fluororesin composite fiber made of fluorine IH resin and TLCP with high strength and high elastic modulus was obtained.

Next, the present fluororesin composite fiber was heated at 240°C in the same manner as in Example 2.
When heat treated for 7 hours under a stream of nitrogen gas, fibers having the following properties were obtained.

■Fineness of resin composite fiber = 15d ■15d9.1 g/d (146kg/m#) ■Elongation -3.4% ■Modulus of elasticity = 290 g/4 (4.7t/J) in 0 fibers Aspect ratio of TLCP = 100 or more (T
Since L CP is continuous, it is practically infinite. ) The number average molecular weight of TLCP was approximately 64,000.

Moreover, the melting point of the TLCP had increased to 335°C. Note that the melting point of the fluororesin remained unchanged.

A fluororesin composite fiber made of a fluororesin and TLCP with high strength and high elastic modulus was obtained by rQll et al.

(Effects of the Invention) The configuration of the present invention brings about the following great effects.

■High-strength, high-modulus fluororesin composites can be stably produced.

■Fluorine (As the strength of the sealant has improved, the uses of fluororesin have expanded.

■TLCP and fluorine! ! (There is less peeling of fat, especially when the resin composite adopts a polymer array structure.

There is particularly little peeling between the two.

(2) In particular, when the fluororesin resin composite of the present invention is subjected to a press treatment or the like and used as a base material for FRP, an FRP with high strength, high modulus of elasticity, chemical resistance, and good sliding properties can be obtained.

■If the resin complex is a polymer array, 'rLC
High IB because the ratio of P and fluororesin is stable in the air
It becomes reliable FRP.

(2) Since the resin composite itself is made into FRP, there is no need to add a matrix polymer afterwards, so there is no uneven addition, and therefore FRP with stable physical properties can be produced. This is particularly good in the case of polymer arrays.

■Since TLCP can be made infusible, it is easy to mold the resin composite into chips or fibers.

■High strength is obtained by heat-treating fluororesin composites at high temperatures.

Since the modulus of elasticity is increased, it becomes a resin composite with even higher strength.

■Resin composite with high weather resistance, high chemical resistance, and high heat resistance.

[Phase] Forms a resin complex that is easy to remove.

Claims (16)

[Claims] (1) A resin composite consisting of at least a thermoplastic liquid crystal resin and a thermoplastic fluororesin, the thermoplastic liquid crystal resin forming a fibrous structure within the fluororesin. Resin resin composite. (2) The fluororesin composite according to claim 1, wherein the thermoplastic liquid crystal resin fibrous material has a diameter of 10 microns or less and an aspect ratio of 10 or more. (3) The fluororesin composite according to claim 1 or 2, wherein the resin composite is a fibrous material. (4) The fluororesin composite according to any one of claims 1 to 3, wherein the resin composite is in the form of a chip. (5) The fluororesin composite according to any one of claims 1 to 4, wherein the liquid crystal resin is a liquid crystal polyester or a liquid crystal polyester amide. (6) Claim 1 wherein the fluororesin is at least one of the following:
6. The fluororesin composite according to any one of . Tetrafluoroethylene, polyfluoroalkoxyethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and ethylene. (7) Claims 1 to 3, wherein the tensile strength is 35 kg/mm or more.
6. The fluororesin composite according to any one of 6. (8) The fluororesin composite according to any one of claims 1 to 7, wherein the liquid crystal resin has a melting point higher than that of the fluororesin by 20°C or more. (9) Claims 1 to 8 wherein the liquid crystal resin fibrous material is infusible.
The fluororesin composite according to any one of. (10) The fluororesin composite according to any one of claims 1 to 9, wherein the liquid crystal resin fibrous material has a number average molecular weight of 13,000 or more. (11) At least an alkali metal salt and/or
The fluororesin composite according to any one of claims 1 to 10, wherein the fluororesin composite contains and/or has an alkaline earth metal salt attached thereto. (12) The fluororesin composite according to any one of claims 1 to 11, wherein at least the liquid crystal resin contains and/or adheres fine particles of at least one metal compound selected from iron, cobalt, and chromium. (13) Melting and molding a liquid crystal resin and a fluororesin to form a resin composite in which the liquid crystal resin exists in the form of fibers in the fluororesin;
A method for producing a fluororesin composite, which is then subjected to high-temperature heat treatment in an inert gas flow having a temperature higher than the glass transition temperature of the liquid crystal resin or in a vacuum. (14) At least an alkali metal salt and/or
Alternatively, a liquid crystal resin containing and/or attached to an alkaline earth metal salt is melt-molded and a fluororesin containing and/or attached to the metal salt is melt-molded to form a resin composite, and then glass rearrangement of the liquid crystal resin is carried out. A method for producing a fluororesin composite characterized by high-temperature heat treatment under a flow of inert gas at a temperature higher than that temperature or in a vacuum. (15) A resin composite consisting of a liquid crystal resin and a fluororesin is heat-treated at a high temperature in an inert gas flow at a temperature higher than the glass transition temperature of the liquid crystal resin or in a vacuum, and then treated at a temperature higher than the melting point of the liquid crystal resin. A method for producing a fluororesin composite characterized by making a liquid crystal resin infusible. (16) At least 5% by weight of fine particles of at least one metal compound selected from iron, cobalt, and chromium are added to at least a liquid crystal resin, and the resin is composited by melt-molding with a fluororesin under vacuum or inert gas. 1. A method for producing a fluororesin composite, which comprises molding a body and then heating the liquid crystal resin at a temperature above (melting point -50) C. and in an oxygen-containing atmosphere to make the liquid crystal resin infusible.